CN115181478A - Graphene modified anticorrosive paint, and preparation method and application thereof - Google Patents

Graphene modified anticorrosive paint, and preparation method and application thereof Download PDF

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Publication number
CN115181478A
CN115181478A CN202210984256.5A CN202210984256A CN115181478A CN 115181478 A CN115181478 A CN 115181478A CN 202210984256 A CN202210984256 A CN 202210984256A CN 115181478 A CN115181478 A CN 115181478A
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silane coupling
modified
coupling agent
graphene oxide
graphene
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CN115181478B (en
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肖双
李琦
王瑛
张立君
冯彩霞
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Shandong Yuhuang New Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a graphene modified anticorrosive paint, a preparation method and application thereof, and relates to the technical field of anticorrosive paints. The graphene modified anticorrosive paint comprises the following components in percentage by mass: 0.1 to 0.2 of a first component and a second component; the first component comprises the following components in parts by weight: 100 parts of epoxy resin, 2-4 parts of reduced graphene oxide modified by a silane coupling agent, 4-5 parts of nano ceramic powder, 0.1-0.5 part of defoaming agent and 0.5-1 part of flatting agent; the second component comprises the following components: 100 to 150 portions of amine curing agent, 1 to 5 portions of defoaming agent and 5 to 10 portions of flatting agent. The anticorrosive coating in the application enables the graphene plane to reduce agglomeration phenomenon in a film-forming carrier and promotes the graphene plane to be uniformly distributed, effectively prolongs the contact path of corrosion factors such as water and oxygen molecules with a protected substrate, and improves the anticorrosive property of the coating.

Description

Graphene modified anticorrosive paint, and preparation method and application thereof
Technical Field
The invention relates to the field of anticorrosive coatings, and in particular relates to a graphene modified anticorrosive coating, and a preparation method and application thereof.
Background
Corrosion is a slow chemical or electrochemical process, which refers to a natural phenomenon that a metal material fails and is destroyed due to the action of oxygen, water and the like. The problems of bridge collapse, ship wrecking, workshop equipment damage and the like caused by metal corrosion bring huge loss to daily life and production of people.
The common metal protection technologies mainly comprise cathodic protection, corrosion inhibitor protection, metal plating, surface organic coating and the like. Wherein the organic coating on the surface is the most common and effective corrosion prevention mode which is the highest in global corrosion prevention cost. Therefore, by researching the mechanism of metal corrosion, the search for effective organic anticorrosive coatings to protect metals so as to retard the corrosion rate of metals, and therefore, the reduction of the harm caused by corrosion is a hot and necessary technical problem.
Graphene is a two-dimensional material with a single-layer sheet structure, has a thickness of only one atomic diameter (about 0.35 nm), and is a star material which is of great interest and has wide application prospects. The single-layer defect-free graphene coating has excellent shielding performance, can prevent corrosion factors such as oxygen, water molecules and the like from reaching the surface of a metal matrix, and has excellent thermal, electrical and mechanical properties, so that a lot of researches on the application of graphene to the field of anticorrosive coatings are carried out nowadays.
Graphene itself is inert to reaction and van der waals interaction causes irreversible accumulation, making it insoluble in water and common organic solvents and more difficult to complex with organic or inorganic materials, which is the biggest obstacle of graphene as a filler for composite materials, and secondly, defect-free graphene is difficult to prepare and difficult to apply in industrial mass production.
The graphene oxide can be prepared from graphite in a large scale, and the graphene oxide plane has a large number of hydrophilic functional groups and has good wetting property and surface activity, so that the graphene oxide can be dispersed in dilute alkaline water and pure water to form stable colloidal suspension; however, in the process of preparing the composite organic material, the graphene oxide is still agglomerated in a large amount due to the action of polar groups and extremely large specific surface area and is difficult to be uniformly distributed in the organic material, so that the performance of the composite material is reduced.
Therefore, in the field of preparing the anticorrosive paint by using graphene, how to uniformly distribute the graphene material in the anticorrosive paint to prolong the contact path of corrosion factors such as water and oxygen molecules and the like with a protected substrate and reduce electrochemical corrosion reaction caused by accumulation has important significance in improving the anticorrosive performance of the paint.
Disclosure of Invention
In order to solve the above problems, a first object of the present invention is to provide a graphene modified anticorrosive coating, the graphene modified anticorrosive coating utilizes a silane coupling agent to modify graphene oxide and uses vitamin C to reduce the graphene oxide, and the silane coupling agent modified graphene oxide, a film-forming carrier epoxy resin and filler nano ceramic powder are matched with each other, so that the aggregation of graphene planes in the epoxy resin can be effectively reduced, the uniform dispersion effect of the graphene planes can be improved, and the anticorrosive performance of the coating can be improved.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the graphene modified anticorrosive paint comprises the following components in percentage by mass of 1:0.1 to 0.2 of a first component and a second component; based on the weight portion of the raw materials,
the first component comprises the following components: 100 parts of epoxy resin, 2-4 parts of reduced graphene oxide modified by a silane coupling agent, 4-5 parts of nano ceramic powder, 0.1-0.5 part of defoaming agent and 0.5-1 part of flatting agent;
the second component comprises the following components: 100 to 150 parts of amine curing agent, 1 to 5 parts of defoaming agent and 5 to 10 parts of flatting agent.
The graphene modified anticorrosive paint provided by the invention comprises components such as epoxy resin, silane coupling agent modified reduced graphene oxide and nano ceramic powder, wherein the silane coupling agent modified reduced graphene oxide has a polar group and an organic functional group, and the organic functional group can perform a coupling reaction with the epoxy resin to enable a graphene plane and macromolecules in the epoxy resin to be tightly connected through a rope effect of the silane coupling agent, so that the separation and uniform distribution of the graphene plane in a mixing process are effectively promoted. The silane coupling agent modified reduced graphene oxide can interact with the nano ceramic powder and is bonded by weak intermolecular force, so that the silane coupling agent modified reduced graphene oxide and the nano ceramic powder can be uniformly dispersed in the anticorrosive paint. In addition, the coating added with the nano ceramic powder has better mechanical property, blocks pores and improves the corrosion resistance.
In the invention, the silane coupling agent modified reduced graphene oxide is prepared from graphene oxide slurry, a silane coupling agent and vitamin C.
According to the graphene modified anticorrosive coating, the silane coupling agent modified reduced graphene oxide is subjected to surface grafting modification by using the silane coupling agent and is reduced by using the vitamin C, so that the extremely large specific surface area of graphene oxide planes is reduced, the action distance of pi-pi bonds between the graphene oxide planes is increased, and the phenomenon of attraction and agglomeration between the graphene oxide planes can be effectively prevented; the silane coupling agent modified graphene oxide plane has polar groups which are not modified by silane coupling agent grafting, attraction among the polar groups still leads to the joint of the exposed part of the graphene plane, and the vitamin C is used for reducing the graphene oxide grafted by the silane coupling agent, so that on one hand, the agglomeration force among the graphene oxide planes is weakened, the joint is reduced, and the dispersion of the graphene planes is promoted, on the other hand, the reduced graphene oxide plane has better quality, has stronger barrier property on corrosion factors such as water, oxygen molecules and the like, and further improves the corrosion resistance of the coating.
In the invention, the mass ratio of the graphene oxide slurry to the silane coupling agent is 1:2 to 4.
The organic functional groups of the silane coupling agent have weak coupling effect, so the proportion of the silane coupling agent and the graphene oxide slurry is very critical, and the organic functional groups of the silane coupling agent are accumulated due to excessive silane coupling agent, so that a super-large spherical aggregate of the inner silane coupling agent and the outer graphene oxide plane can be formed; too little silane coupling agent can cause insufficient grafting quantity of graphene oxide planes, and the graphene oxide planes with smooth baldness can be agglomerated in a large quantity, so that the uniform dispersion effect is influenced.
In the invention, the silane coupling agent comprises one or more of KH550 and KH 560;
preferably, the silane coupling agent comprises KH550 and KH560, and the mass ratio of KH550 to KH560 is 1:4 to 6.
The silane coupling agent KH560 and the epoxy resin are both soft acidic, and KH550 is weakly alkaline, and can slowly react with the epoxy resin to reduce the preservation time of the anticorrosive coating, but the silane coupling agent KH550 and KH560 are used according to the specific proportion, and an-NH bond generated by the reaction of active groups of the silane coupling agent KH550 and the epoxy resin can react with epoxy resin molecules to form a tight chemical bond, so that the connection effect of the silane coupling agent as a rope is improved.
In the invention, the nano ceramic powder comprises one or more of nano silicon carbide, nano aluminum oxide and nano zirconium oxide.
The nano ceramic powder is a material with small volume, large density and stable property, and can be combined with an oxygen-containing polar group which is not reduced on a reduced graphene oxide plane and is modified by a silane coupling agent and a polar group of the silane coupling agent on the graphene oxide plane, so that on one hand, the polar group of the graphene oxide plane can be further shielded to reduce agglomeration, and on the other hand, the nano ceramic powder can be used as a weight carrier of the graphene plane, and the disassembly of an inner silane coupling agent and an outer oxidized graphene plane spherical aggregate formed by the organic functional agglomeration of the silane coupling agent is effectively promoted; in the application process of coating the anticorrosive paint, the graphene oxide plane tends to be stabilized in the horizontal direction due to the gravity sinking effect of the nano ceramic material counterweight carrier, so that the utilization efficiency of the graphene oxide plane for prolonging the contact path of water, oxygen and a protected substrate is improved, and the anticorrosive performance of the paint is effectively improved.
Preferably, the nano ceramic powder comprises nano alumina and nano zirconia, and the mass ratio of the nano alumina to the nano zirconia is 1-3: 1.
nanometer zirconia compares nanometer alumina more stable and density is higher, and the ratio of above-mentioned nanometer zirconia and nanometer alumina makes, and the oxidation graphite alkene among the anticorrosive coating can not influence the corrosion resisting property because of the excessive deposit in the coating lower floor of oxidation graphite alkene plane that nanometer zirconia leads to, also can not lead to the oxidation graphite alkene plane reunion phenomenon that the counter weight carrier effect is poor to lead to because of nanometer alumina.
In the invention, the epoxy resin is one or more of polyether modified epoxy resin and novolac epoxy resin.
The polyether modified epoxy resin and the novolac epoxy resin are used as film forming carriers of the coating, the polarity is weak before the coating is not cured, the polarity effect of the reduced graphene oxide and the nano ceramic powder modified by the silane coupling agent cannot be influenced, and the epoxy resin can be coupled with organic functional groups of the silane coupling agent to generate close chemical bonding, so that the dispersion and the uniform distribution of graphene planes are promoted.
In the invention, the amine curing agent is one or more of polyamide curing agent and polyether amine curing agent.
The invention provides a preparation method of the graphene modified anticorrosive paint, which comprises the following steps:
(1) Dispersing the graphene oxide slurry into a silane coupling agent, adding DCC (DCC-type metal oxide) and performing ultrasonic dispersion treatment for 20-40 min, and then placing the mixture in a water bath kettle at the temperature of 55-65 ℃ to uniformly stir and react for 5-7 h to obtain silane coupling agent modified graphene oxide;
(2) Adding the silane coupling agent modified graphene oxide obtained in the step (1) into a DMF (dimethyl formamide) solvent under an ultrasonic condition, adding ammonia water for uniform dispersion, adding vitamin C for adjusting the pH to 6-7, carrying out reduction reaction for 4-6 h at 75-95 ℃, washing with pure water, and drying under vacuum to obtain the silane coupling agent modified reduced graphene oxide;
(3) Uniformly mixing the reduced graphene oxide modified by the silane coupling agent, epoxy resin, nano ceramic powder, a defoaming agent and a flatting agent to obtain a first component;
(4) And (3) uniformly mixing the amine curing agent, the defoaming agent and the flatting agent to obtain a second component.
In the invention, the mixing mode of the first component in the step (3) is one of high-speed dispersion, ball milling and mechanical stirring. Preferably, the mixing is by high speed dispersion.
Preferably, before the step (3), the obtained silane coupling agent modified reduced graphene oxide and nano ceramic powder are pulverized in an ultrafine pulverizer, and then are mixed with the rest of the components in the step (3) to obtain the first component.
The invention also provides application of the graphene modified anticorrosive paint in the field of metal corrosion prevention.
The invention has the following beneficial effects:
1. according to the method, the silane coupling agent is grafted to the plane and the edge of the graphene oxide through the modification operation of the silane coupling agent of the graphene oxide, so that the specific surface area of the graphene oxide is reduced, the action distance between the graphene oxides is increased, and the agglomeration of the graphene oxide in epoxy resin is reduced; on the other hand, the oily group of the silane coupling agent can form an abnormally tight chemical bond combination with the epoxy resin, so that the modified graphene oxide is separated from an agglomeration state along with the traction of the epoxy resin in the subsequent high-speed dispersion fusion stage, and the effect of uniform distribution is achieved.
2. In the application, the graphene oxide modified by the silane coupling agent is reduced, the C/O ratio of the graphene oxide is increased, and polar groups on the surface and the edge are reduced, so that the polar group attraction between the graphene oxides is reduced, the reduced graphene oxide is higher in plane quality, and corrosion factors such as water, oxygen molecules and the like are more difficult to contact with a protected substrate.
3. According to the method, the nano ceramic powder is used for the silane coupling agent modified reduced graphene oxide, and can be used as a counterweight with high density and small volume to be attached to the modified reduced graphene oxide, so that the dispersion effect of the graphene oxide plane is obviously enhanced in the mixing stage; and the nano ceramic powder is used as a nano material, and can effectively fill pores in the coating when added into the anticorrosive coating, block water and oxygen, thereby improving the anticorrosive property of the coating and improving the mechanical property of the coating.
Detailed Description
In order to further explain the technical means adopted by the present invention and the effects thereof, the present invention is further explained by combining with the embodiments below. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or apparatus used are conventional products commercially available from normal sources, not indicated by the manufacturer.
Example 1
(1) Preparing the silane coupling agent modified graphene oxide: dispersing 10g of graphene oxide slurry prepared in a graphene workshop into 20g of silane coupling agent KH560, adding 5ml of DCC as a grafting modification promoter, treating for 20min at 30kHz by using an ultrasonic dispersion mode, and then uniformly stirring and reacting for 5h in a water bath kettle at 55 ℃ to obtain silane coupling agent modified graphene oxide;
(2) Preparing reduced graphene oxide modified by a silane coupling agent: ultrasonically dispersing the silane coupling agent modified graphene oxide obtained in the step (1) into 30ml of DMF solvent, adding 2ml of 25% concentrated ammonia water serving as a reduction reaction promoter, then adding vitamin C to adjust the pH value to 6, carrying out reduction reaction for 4h at the temperature of 75 ℃, washing with pure water, and drying under vacuum to obtain the silane coupling agent modified reduced graphene oxide;
(3) Preparation of the first component: mixing 20g of the reduced graphene oxide modified by the silane coupling agent with 1kg of polyether modified epoxy resin, 40g of nano zirconia, 1g of defoaming agent BYK-A530 and 5g of flatting agent BKY-306, and then placing the mixture on a high-speed dispersion machine for high-speed dispersion for 5 hours to uniformly fuse to obtain a first component;
(4) Preparation of the second component: 100g of polyamide curing agent NT-1545, 1g of defoaming agent BYK-A530 and 5g of flatting agent BYK-306 are uniformly stirred and mixed to obtain a second component.
Example 2
(1) Preparing the graphene oxide modified by the silane coupling agent: dispersing 10g of graphene oxide slurry prepared in a graphene workshop into 40g of silane coupling agent KH560, adding 5ml of DCC as a grafting modification promoter, treating for 40min at 30kHz by using an ultrasonic dispersion mode, and then uniformly stirring and reacting for 7h in a 65 ℃ water bath to obtain silane coupling agent modified graphene oxide;
(2) Preparing reduced graphene oxide modified by a silane coupling agent: ultrasonically dispersing the silane coupling agent modified graphene oxide obtained in the step (1) into 30ml of DMF solvent, adding 2ml of 25% concentrated ammonia water serving as a reduction reaction promoter, then adding vitamin C to adjust the pH to 7, carrying out reduction reaction for 6h at the temperature of 95 ℃, washing with pure water, and drying under vacuum to obtain the silane coupling agent modified reduced graphene oxide;
(3) Preparation of the first component: mixing 40g of the reduced graphene oxide modified by the silane coupling agent with 1kg of novolac epoxy resin, 10g of nano-zirconia, 30g of nano-alumina, 5g of defoaming agent BYK-A530 and 10g of flatting agent BKY-306, and then placing the mixture on a high-speed dispersion machine for high-speed dispersion for 5 hours to uniformly fuse to obtain a first component;
(4) Preparation of the second component: and uniformly stirring and mixing 120g of polyetheramine curing agent D-230, 1g of defoaming agent BYK-A530 and 5g of flatting agent BYK-306 to obtain a second component.
Example 3
(1) Preparing the graphene oxide modified by the silane coupling agent: dispersing 10g of graphene oxide slurry prepared in a graphene workshop into a mixed solution of 25g of a silane coupling agent KH560 and 5g of a silane coupling agent KH550, adding 5ml of DCC as a grafting modification promoter, treating for 40min at 30kHz by using an ultrasonic dispersion mode, and then placing in a water bath kettle at 60 ℃ to uniformly stir and react for 7h to obtain graphene oxide modified by the silane coupling agent;
(2) Preparing reduced graphene oxide modified by a silane coupling agent: ultrasonically dispersing the silane coupling agent modified graphene oxide obtained in the step (1) into 30ml of DMF solvent, adding 2ml of 25% concentrated ammonia water serving as a reduction reaction promoter, then adding vitamin C to adjust the pH to 7, carrying out reduction reaction for 5 hours at the temperature of 95 ℃, washing with pure water, and drying under vacuum to obtain the silane coupling agent modified reduced graphene oxide;
(3) Preparation of the first component: mixing 30g of the reduced graphene oxide modified by the silane coupling agent with 1kg of phenolic epoxy resin, 10g of nano-zirconia, 20g of nano-alumina, 20g of nano-silicon carbide, 2g of defoaming agent BYK-A500 and 6g of flatting agent BYK-320, and then placing the mixture on a high-speed dispersion machine for high-speed dispersion for 5 hours to uniformly fuse to obtain a first component;
(4) Preparation of the second component: 150g of polyamide curing agent NT-1545, 2g of defoaming agent BYK-A500 and 6g of flatting agent BYK-320 are uniformly stirred and mixed to obtain a second component.
Example 4
(1) Preparing the silane coupling agent modified graphene oxide: dispersing 10g of graphene oxide slurry prepared in a graphene workshop into 30g of silane coupling agent KH560, adding 5ml of DCC as a grafting modification promoter, treating for 40min at 30kHz by using an ultrasonic dispersion mode, and then uniformly stirring and reacting for 7h in a water bath kettle at 60 ℃ to obtain silane coupling agent modified graphene oxide;
(2) Preparing reduced graphene oxide modified by a silane coupling agent: ultrasonically dispersing the silane coupling agent modified graphene oxide obtained in the step (1) into 30ml of DMF solvent, adding 3ml of 25% concentrated ammonia water serving as a reduction reaction promoter, then adding vitamin C to adjust the pH to 7, carrying out reduction reaction for 6h at the temperature of 80 ℃, washing with pure water, and drying under vacuum to obtain the silane coupling agent modified reduced graphene oxide;
(3) Preparation of the first component: mixing 40g of the reduced graphene oxide modified by the silane coupling agent with 1kg of polyether modified epoxy resin, 25g of nano-zirconia, 25g of nano-alumina, 3g of defoaming agent BYK-A500 and 5g of flatting agent BYK-320, and then placing the mixture on a high-speed dispersion machine for high-speed dispersion for 5 hours to uniformly fuse to obtain a first component;
(4) Preparation of the second component: and uniformly stirring and mixing 130g of polyetheramine curing agent D-230, 3g of defoaming agent BYK-A500 and 5g of flatting agent BYK-320 to obtain a second component.
Example 5
(1) Preparing the silane coupling agent modified graphene oxide: dispersing 10g of graphene oxide slurry prepared in a graphene workshop into 40g of silane coupling agent KH560, adding 5ml of DCC as a grafting modification promoter, treating for 20min at 30kHz by using an ultrasonic dispersion mode, and then uniformly stirring and reacting for 5h in a water bath kettle at 55 ℃ to obtain silane coupling agent modified graphene oxide;
(2) Preparing reduced graphene oxide modified by a silane coupling agent: ultrasonically dispersing the silane coupling agent modified graphene oxide obtained in the step (1) into 30ml of DMF solvent, adding 2ml of 25% concentrated ammonia water serving as a reduction reaction promoter, then adding vitamin C to adjust the pH value to 6, carrying out reduction reaction for 4h at the temperature of 75 ℃, washing with pure water, and drying under vacuum to obtain the silane coupling agent modified reduced graphene oxide;
(3) Pretreating modified graphene and nano ceramic powder: taking 30g of the reduced graphene oxide modified by the silane coupling agent in the step (2), 20g of nano-zirconia and 40g of nano-alumina, and further refining and grinding in an ultrafine grinder to obtain a modified graphene-nano ceramic powder mixture with smaller particle size;
(4) Preparation of the first component: mixing 40g of the modified graphene-nano ceramic powder mixture obtained in the step (3) with 1kg of polyether modified epoxy resin, 1g of defoaming agent BYK-A530 and 8g of flatting agent BKY-306, and then placing the mixture on a high-speed dispersion machine for high-speed dispersion for 5 hours to uniformly fuse to obtain a first component;
(5) Preparation of the second component: and uniformly stirring and mixing 150g of polyetheramine curing agent D-230, 1g of defoaming agent BYK-A530 and 8g of flatting agent BYK-306 to obtain a second component.
Comparative example 1
(1) Preparation of the first component: mixing 40g of graphene oxide slurry prepared in a graphene workshop with 1kg of novolac epoxy resin, 10g of nano-zirconia, 30g of nano-alumina, 5g of defoaming agent BYK-A530 and 10g of flatting agent BKY-306, and then placing the mixture on a high-speed dispersion machine for high-speed dispersion for 5 hours to uniformly fuse to obtain a first component;
(4) Preparation of the second component: and uniformly stirring and mixing 120g of polyetheramine curing agent D-230, 1g of defoaming agent BYK-A530 and 5g of flatting agent BYK-306 to obtain a second component.
Comparative example 2
(1) Preparing the silane coupling agent modified graphene oxide: dispersing 10g of graphene oxide slurry prepared in a graphene workshop into 40g of silane coupling agent KH560, adding 5ml of DCC as a grafting modification promoter, treating for 40min at 30kHz by using an ultrasonic dispersion mode, and then uniformly stirring and reacting for 7h in a 65 ℃ water bath to obtain silane coupling agent modified graphene oxide;
(2) Preparing reduced graphene oxide modified by a silane coupling agent: ultrasonically dispersing the silane coupling agent modified graphene oxide obtained in the step (1) into 30ml of DMF solvent, adding 2ml of 25% concentrated ammonia water serving as a reduction reaction promoter, then adding vitamin C to adjust the pH to 7, carrying out reduction reaction for 6h at the temperature of 95 ℃, washing with pure water, and drying under vacuum to obtain the silane coupling agent modified reduced graphene oxide;
(3) Preparation of the first component: mixing 40g of the reduced graphene oxide modified by the silane coupling agent with 1kg of phenolic epoxy resin, 5g of defoaming agent BYK-A530 and 10g of flatting agent BKY-306, and then placing the mixture on a high-speed dispersion machine for high-speed dispersion for 5 hours to uniformly fuse to obtain a first component;
(4) Preparation of the second component: and uniformly stirring and mixing 120g of polyetheramine curing agent D-230, 1g of defoaming agent BYK-A530 and 5g of flatting agent BYK-306 to obtain a second component.
Comparative example 3
(1) Preparation of the first component: mixing 1kg of novolac epoxy resin with 10g of nano-zirconia, 30g of nano-alumina, 5g of defoaming agent BYK-A530 and 10g of flatting agent BKY-306, and then placing the mixture on a high-speed dispersion machine for high-speed dispersion for 5 hours to uniformly fuse to obtain a first component;
(4) Preparation of the second component: and uniformly stirring and mixing 120g of polyetheramine curing agent D-230, 1g of defoaming agent BYK-A530 and 5g of flatting agent BYK-306 to obtain a second component.
Experimental example 1
The first component in the graphene anti-corrosive paint prepared in examples 1 to 5 and comparative examples 1 to 2 was subjected to particle size analysis and centrifugal stability test to evaluate the distribution of the graphene material, wherein the graphene material was centrifuged at 6000r/min for 20min in the centrifugal stability test, and the results are shown in table 1.
TABLE 1
Figure BDA0003801415980000101
Figure BDA0003801415980000111
Experimental example 2
The graphene anticorrosive coatings prepared in examples 1 to 5 and comparative examples 1 to 2 were sprayed in the following spraying manner, and the adhesion, impact strength, hardness, and long-term neutral salt spray resistance of the coating were tested, and the results are shown in table 2.
The spraying method comprises the following steps:
(1) Pretreating tinplate: grinding the tinplate by using 500-mesh abrasive paper, ultrasonically cleaning the base material by using acetone, and finally ultrasonically cleaning and drying by using ethanol to obtain the surface of the base material with oil stains on the surface for later use;
(2) The first component and the second component of the anticorrosive paint in the examples or the comparative examples are mixed according to the weight ratio of 1:0.2, uniformly stirring, spraying, placing the sprayed base material in an oven at 80 ℃ for curing for 1h, and further reacting epoxy and a curing agent to form a uniform and stable coating, wherein the pressure of a spraying vacuum pump is 5bar, and the spraying thickness is 50-55 mu m.
The hardness improvement effect of the prepared coating is judged according to the hardness of the paint film measured by the GB/T6739-2006 pencil method.
The adhesion properties of the coatings were tested according to GB/T9286-1998 test methods for cross-hatch of varnishes, paints and lacquers.
The corrosion performance of the coating was determined by manually simulating salt spray environmental conditions according to GB/T10125-2012. Specifically, the electrochemical alternating-current impedance technology is adopted to carry out the test by using a three-electrode system: wherein the reference electrode is a silver/silver chloride electrode, the counter electrode is a platinum sheet electrode,the test sample is a working electrode, and the electrolyte is 3.5wt% of NaCl solution; after the open-circuit potential of the coating is stabilized, the frequency range of the test is set to be 10 -2 ～10 5 Hz, 20mV of AC voltage amplitude, and 60 days of test period.
TABLE 2
Figure BDA0003801415980000121
As can be seen from table 1, the first component containing the graphene material in the graphene modified anticorrosive coating of the present invention has a smaller average particle size than the comparative example, and has strong centrifugal stability, thereby effectively reducing the agglomeration of the graphene material and improving the uniform dispersion effect of the graphene material. As can be seen from table 2, the graphene modified anticorrosive coating provided by the invention has significantly improved long-term performance in salt spray resistance, and it can be seen that the uniform distribution of the graphene oxide material actually effectively prolongs the contact path between the corrosion factor and the substrate in the salt spray environment, thereby significantly improving the anticorrosive performance of the coating.
Those not described in detail in this specification are within the skill of the art. The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.

Claims (10)

1. The graphene modified anticorrosive paint is characterized by comprising the following components in percentage by mass of 1:0.1 to 0.2 of a first component and a second component; based on the weight portion, the weight portion of the material,
the first component comprises the following components: 100 parts of epoxy resin, 2-4 parts of reduced graphene oxide modified by a silane coupling agent, 4-5 parts of nano ceramic powder, 0.1-0.5 part of defoaming agent and 0.5-1 part of flatting agent;
the second component comprises the following components: 100 to 150 portions of amine curing agent, 1 to 5 portions of defoaming agent and 5 to 10 portions of flatting agent.
2. The graphene modified anticorrosive paint according to claim 1, wherein the silane coupling agent modified reduced graphene oxide is prepared from graphene oxide slurry, a silane coupling agent and vitamin C.
3. The graphene modified anticorrosive paint according to claim 2, wherein the mass ratio of the graphene oxide slurry to the silane coupling agent is 1:2 to 4.
4. The graphene modified anticorrosive coating according to claim 3, wherein the silane coupling agent comprises one or more of KH550 and KH 560.
5. The graphene modified anticorrosive paint according to any one of claims 1 to 4, wherein the nano ceramic powder comprises one or more of nano silicon carbide, nano aluminum oxide and nano zirconium oxide;
preferably, the nano ceramic powder comprises nano alumina and nano zirconia, and the mass ratio of the nano alumina to the nano zirconia is 1-3: 1.
6. the graphene modified anticorrosive paint according to any one of claims 1 to 4, wherein the epoxy resin is one or more of polyether modified epoxy resin and novolac epoxy resin.
7. The graphene modified anticorrosive paint according to any one of claims 1 to 4, wherein the amine curing agent is one or more of a polyamide curing agent and a polyether amine curing agent.
8. The preparation method of the graphene modified anticorrosive paint according to any one of claims 1 to 7, characterized by comprising the following steps:
(1) Dispersing the graphene oxide slurry into a silane coupling agent, adding DCC (DCC-type metal oxide) and performing ultrasonic dispersion treatment for 20-40 min, and then placing the mixture in a water bath kettle at the temperature of 55-65 ℃ to uniformly stir and react for 5-7 h to obtain silane coupling agent modified graphene oxide;
(2) Adding the silane coupling agent modified graphene oxide obtained in the step (1) into a DMF (dimethyl formamide) solvent under an ultrasonic condition, adding ammonia water for uniform dispersion, adding vitamin C for adjusting the pH to 6-7, carrying out reduction reaction for 4-6 h at 75-95 ℃, washing with pure water, and drying under vacuum to obtain the silane coupling agent modified reduced graphene oxide;
(3) Uniformly mixing the reduced graphene oxide modified by the silane coupling agent, epoxy resin, nano ceramic powder, a defoaming agent and a flatting agent to obtain a first component;
(4) And (3) uniformly mixing the amine curing agent, the defoaming agent and the flatting agent to obtain a second component.
9. The preparation method of the graphene modified anticorrosive paint according to claim 8, wherein the reduced graphene oxide modified by the silane coupling agent and the nano ceramic powder are pulverized in an ultrafine pulverizer before the step (3), and then are mixed with the rest of the components in the step (3) to obtain the first component.
10. The application of the graphene modified anticorrosive paint of any one of claims 1 to 7 in the field of metal corrosion prevention.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115838545A (en) * 2022-12-12 2023-03-24 福州大学 Preparation method of multi-layer assembled poly-o-aminophenol modified graphene/waterborne polyurethane composite coating
CN116285570A (en) * 2023-02-22 2023-06-23 沈阳工业大学 Epoxy resin modified cold zinc spraying coating and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106952675A (en) * 2017-03-22 2017-07-14 西北大学 Graphene-based organic carrier and preparation method thereof, electric slurry and preparation method thereof
CN111944390A (en) * 2020-07-31 2020-11-17 中国石油天然气集团有限公司 Modified phenolic epoxy coating and preparation method and application thereof
CN112080187A (en) * 2020-08-28 2020-12-15 中国石油天然气股份有限公司 Graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention and preparation method thereof
CN112778869A (en) * 2019-11-05 2021-05-11 宜兴汉光高新石化有限公司 Water-based two-component epoxy anticorrosive paint for storage tank weld joint and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106952675A (en) * 2017-03-22 2017-07-14 西北大学 Graphene-based organic carrier and preparation method thereof, electric slurry and preparation method thereof
CN112778869A (en) * 2019-11-05 2021-05-11 宜兴汉光高新石化有限公司 Water-based two-component epoxy anticorrosive paint for storage tank weld joint and preparation method thereof
CN111944390A (en) * 2020-07-31 2020-11-17 中国石油天然气集团有限公司 Modified phenolic epoxy coating and preparation method and application thereof
CN112080187A (en) * 2020-08-28 2020-12-15 中国石油天然气股份有限公司 Graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115838545A (en) * 2022-12-12 2023-03-24 福州大学 Preparation method of multi-layer assembled poly-o-aminophenol modified graphene/waterborne polyurethane composite coating
CN116285570A (en) * 2023-02-22 2023-06-23 沈阳工业大学 Epoxy resin modified cold zinc spraying coating and preparation method thereof

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